JP6845752B2 - Paint resins, paint dispersants, paint base resins, paint compositions and coatings - Google Patents

Description

The present invention relates to a paint resin, a paint dispersant, a paint base resin, a paint composition and a coating film, and more specifically, a paint resin, a paint dispersant composed of the paint resin, a paint base resin composed of the paint resin, and a paint resin. The present invention relates to a coating composition containing the coating composition and a coating film comprising the coating composition.

Conventionally, in a coating composition, an acrylic resin has been used as a base resin, a pigment dispersant, and the like.

As the base resin, for example, an epoxy ester resin composition (a) and an alkyd resin composition (b) having an oil length of 40 to 70% are mixed, and methyl methacrylate, styrene, and perbenzoic acid t- A resin composition (A) obtained by adding and reacting an acrylic monomer (c) such as butyl has been proposed (see, for example, Patent Document 1).

Examples of the pigment dispersant include (1) a (meth) acrylic acid ester having a saturated alicyclic group composed of two or more rings, and (2) an alkyl ester of C10 to C35 of (meth) acrylic acid. , (3) A copolymer obtained by polymerizing a polymerizable monomer containing at least one functional group selected from a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium base, a sulfonic acid group, and a phosphoric acid group. The content of the monomer (1) constituting the copolymer (A) containing (A) as an active ingredient is 5 to 60% by weight, the monomer (2) is 5 to 50% by weight, and the monomer (3) is 0.1. A resin for dispersing a pigment having a weight of about 30% by weight has been proposed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 10-077442 Japanese Unexamined Patent Publication No. 2007-238643

On the other hand, the coating composition is required to use a low-polarity solvent (weak solvent) as the solvent from the viewpoint of workability, environmental friendliness, etc., and the resin (base resin, pigment) contained in the coating composition is required. As a dispersant or the like (hereinafter referred to as a paint resin)), dilutability with a low-polarity solvent (weak solvent) is required. However, the paint resins described in Patent Documents 1 and 2 may not be sufficiently dilutable with a weak solvent.

Further, the paint resin may be required to have compatibility with other resins. However, the paint resins described in Patent Documents 1 and 2 may not have sufficient compatibility with other resins.

INDUSTRIAL APPLICABILITY The present invention relates to a paint resin having dilutability with a weak solvent and compatibility with other resins, a paint dispersant made of the paint resin, a paint base resin made of the paint resin, and a paint composition containing the paint resin. And a coating film composed of a coating composition.

The present invention [1] is a coating resin containing an alkido-acrylic resin, wherein the alkido-acrylic resin is a alkido resin having an oxidative polymerizable group and a polymerizable monomer that can be graft-polymerized with respect to the alkido resin. It is a graft polymer with a component, and the polymerizable monomer component is (A) a ring structure-containing (meth) acrylate, (B) an alkyl (meth) acrylate having an alkyl group having 10 to 35 carbon atoms, and (C). ) A coating resin containing styrenes and (D) at least one of a carboxyl group-terminated-monofunctional (meth) acrylic compound represented by the following (d1) to (d3).

(D1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).

CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1)
(In the formula (1), R ¹ represents a hydrogen atom and a methyl group, and n represents 1 to 10).
(D2) An acid anhydride modified product of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).

CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2)
(In the formula (2), R ¹ represents a hydrogen atom and a methyl group, R ² represents at least one selected from the group consisting of an ethylene group, a propylene group and a tetramethylene group, and n represents 1 to 1. 10 is shown.)
(D3) An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).

CH ₂ = C (R ¹ ) COO ( _Cm H _2m O) _n H (3)
(In formula (3), R ¹ represents a hydrogen atom and a methyl group, m represents 2 to 4, and n represents 1 to 10.)
In the present invention [2], (D) the carboxyl group-terminated-monofunctional (meth) acrylic compound contains (d1) a caprolactone adduct of (meth) acrylic acid represented by the above formula (1). ] Contains the paint resin described in.

In the present invention [3], the above-mentioned [3], wherein the polymerizable monomer component further contains a carboxyl group-containing polymerizable monomer (however, (D) the carboxyl group terminal-monofunctional (meth) acrylic compound is excluded). It contains the coating resin according to 1] or [2].

In the present invention [4], the coating resin according to any one of the above [1] to [3], wherein the polymerizable monomer component further contains a hydroxyl group-containing polymerizable monomer.

In the present invention [5], any of the above [1] to [4], wherein the polymerizable monomer component further contains a tertiary amino group-containing polymerizable monomer and / or a quaternary ammonium group-containing polymerizable monomer. Contains the paint resin described in item 1.

In the present invention [6], the content ratio of (D) the carboxyl group terminal-monofunctional (meth) acrylic compound is 0.5% by mass or more and 3.0% by mass or less with respect to the total amount of the polymerizable monomer component. The paint resin according to any one of the above [1] to [5] is contained.

The present invention [7] is any one of the above [1] to [6], wherein the alkyd resin is 1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monomer component. Contains the paint resin described in.

The present invention [8] contains a paint dispersant containing the paint resin according to any one of the above [1] to [7].

The present invention [9] includes a paint-based resin containing the paint resin according to any one of the above [1] to [7].

The present invention [10] includes a coating composition containing the coating resin according to any one of the above [1] to [7].

The present invention [11] includes a coating film which is a cured product of the coating composition according to the above [10].

The paint resin, paint dispersant, paint base resin, paint composition, and coating film of the present invention contain an alkyd-acrylic resin in which a polymerizable monomer component is polymerized with respect to an alkyd resin, and can be graft-polymerized thereof. Since the polymerizable monomer component contains the above components (A) to (D), it can have both dilutability with a weak solvent and compatibility with other resins.

The paint resin of the present invention contains an alkyd-acrylic resin, and is preferably made of an alkyd-acrylic resin.

The alkyd-acrylic resin is a graft polymer of an alkyd resin and a polymerizable monomer component (including an alkyl (meth) acrylate described later) that can be graft-polymerized with the alkyd resin.

As the alkyd resin, an alkyd resin having an oxidatively polymerizable group is used.

The oxidatively polymerizable group is a group having an oxidatively polymerizable multiple bond, and examples thereof include unsaturated carbon bonds (carbon double bonds or carbon triple bonds) derived from unsaturated fatty acids and / or fats and oils.

That is, an alkyd resin having an oxidatively polymerizable group can be obtained by introducing an unsaturated carbon bond derived from an unsaturated fatty acid and / or an oil or fat into the alkyd resin.

Specifically, an alkyd resin having an oxidatively polymerizable group can be obtained, for example, by subjecting a polyhydric alcohol, a polybasic acid, an unsaturated fatty acid and / or a fat or oil to a condensation reaction.

Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and hexanediol, and 3 such as glycerin and trimethylolpropane. Convalent alcohols, such as tetrahydric alcohols such as pentaerythritol, and hexahydric alcohols such as dipentaerythritol, mannitol, D-sorbitol and the like can be mentioned. These can be used alone or in combination of two or more.

The polyhydric alcohol is preferably a trihydric alcohol (more preferably glycerin) or a tetravalent alcohol (more preferably pentaerythritol), and more preferably a combination thereof.

When trihydric alcohol and tetrahydric alcohol are used in combination, the ratio of their combination is 100 parts by mass of the total amount of trihydric alcohol and tetrahydric alcohol, for example, 1 part by mass or more, preferably 1 part by mass or more. It is 5 parts by mass or more, for example, 20 parts by mass or less, preferably 15 parts by mass or less. The tetravalent alcohol is, for example, 99 parts by mass or more, preferably 95 parts by mass or more, and for example, 80 parts by mass or less, preferably 85 parts by mass or less.

Examples of the polybasic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, succinic anhydride, maleic acid, maleic anhydride, adipic acid, sebacic acid, tetrahydrophthalic anhydride and the like. These can be used alone or in combination of two or more.

The polybasic acid is preferably phthalic anhydride.

Further, if necessary, a polybasic acid and a monobasic acid can be used in combination.

Examples of the monobasic acid include benzoic acid, t-butylbenzoic acid, hexahydrobenzoic acid, cinnamic acid and the like. These can be used alone or in combination of two or more. The monobasic acid is preferably benzoic acid.

When a polybasic acid and a monobasic acid are used in combination, the ratio of the monobasic acid is usually 0 parts by mass with respect to 100 parts by mass of the total amount of the polybasic acid and the monobasic acid. Excess, for example, 15 parts by mass or less, preferably 10 parts by mass or less.

The unsaturated fatty acid is not particularly limited as long as it is a fatty acid having at least one unsaturated carbon bond in the molecule, and examples thereof include known unsaturated fatty acids.

Preferred examples of unsaturated fatty acids include fatty acids having a relatively high solid iodine value (that is, fatty acids having a relatively large number of unsaturated carbon bonds), and specific examples thereof include dry oil fatty acids and semi-drying oil fatty acids. ..

Although the drying oil fatty acid and the semi-drying oil fatty acid are not strictly distinguished, the drying oil fatty acid is usually a fatty acid having a solid iodine value of 130 or more, and the semi-drying oil fatty acid has a solid iodine value of 100. It is a fatty acid of more than 130 and less than 130.

Examples of dry oil fatty acids and semi-dry oil fatty acids include fish oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, flaxseed oil (linseed oil) fatty acids, tung oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, and eno oils. Fatty acids, hemp seed oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, hygiene acid fatty acids, oleic acid, linoleic acid, linolenic acid, etc. Be done. These can be used alone or in combination of two or more.

Preferred examples of the drying oil fatty acid and the semi-drying oil fatty acid include dehydrated castor oil fatty acid.

Further, if necessary, a drying oil fatty acid and / or a semi-drying oil fatty acid can be used in combination with a non-drying oil fatty acid. The non-drying oil fatty acid is usually a fatty acid having a solid iodine value of less than 100.

Examples of the non-drying oil fatty acid include coconut oil fatty acid, hydrogenated coconut oil fatty acid, palm oil fatty acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like. These can be used alone or in combination of two or more.

When the drying oil fatty acid and / or the semi-drying oil fatty acid and the non-drying oil fatty acid are used in combination, the combined ratio thereof is appropriately set as long as the excellent effect of the present invention is not impaired.

Examples of fats and oils include fats and oils having an unsaturated carbon bond. Specifically, for example, fish oil, dehydrated castor oil, saflower oil, flaxseed oil (linseed oil), tung oil, soybean oil, sesame oil, poppy oil, and eno. Examples thereof include dry or semi-dry oils such as oil, hemp seed oil, grape kernel oil, corn oil, tall oil, sunflower oil, cotton seed oil, walnut oil and rubber seed oil. These can be used alone or in combination of two or more.

As the fat and oil, flaxseed oil (flax oil) is preferable.

These unsaturated fatty acids and / or fats and oils can be used alone or in combination of two or more.

The unsaturated fatty acid and / or fat and oil preferably includes a combination of unsaturated fatty acid and fat and oil.

When unsaturated fatty acids and fats and oils are used in combination, the ratio of the combined use of unsaturated fatty acids and fats and oils is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, based on 100 parts by mass of the total amount of unsaturated fatty acids and fats and oils. For example, it is 40 parts by mass or less, preferably 30 parts by mass or less. The fat and oil is, for example, 60 parts by mass or more, preferably 70 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less.

Further, if necessary, known unsaturated fatty acids and / or fats and oils can be used in combination with saturated fatty acids. When unsaturated fatty acids and / or fats and oils are used in combination with saturated fatty acids, the combined ratio thereof is appropriately set as long as the excellent effects of the present invention are not impaired.

In the production of an alkyd resin having an oxidatively polymerizable group, for example, a polyhydric alcohol, a polybasic acid (further, a monobasic acid to be blended if necessary (the same shall apply hereinafter)), an unsaturated fatty acid and / or a fat or oil (Furthermore, a saturated fatty acid (hereinafter, the same applies) to be blended if necessary) is mixed and subjected to a condensation reaction (and an ester exchange reaction), usually at 170 to 280 ° C. for 3 to 15 hours under normal pressure or pressure.

In this reaction, the blending ratio of the polyhydric alcohol, the polybasic acid, the unsaturated fatty acid and / or the fat and oil was such that the carboxyl group of the polyhydric acid, the unsaturated fatty acid and / or the unsaturated fatty acid were added to 1 mol of the hydroxyl group of the polyhydric alcohol. / Or the total molar amount of the fat and oil with the carboxyl group is, for example, 0.5 mol or more, preferably 0.6 mol or more, and for example, 1.1 mol or less, preferably 1.0 mol or less.

Further, the ratio of the polybasic acid to the unsaturated fatty acid and / or the fat and oil is such that the carboxyl group contained in the polybasic acid is, for example, 50 mol% or more, preferably 50 mol% or more, based on the total molar amount of the carboxyl group contained therein. It is 60 mol% or more, for example, 90 mol% or less, preferably 80 mol% or less.

Further, the carboxyl group contained in the unsaturated fatty acid and / or the fat (total amount) is, for example, 10 mol% or more, preferably 20 mol% or more, for example, 50 mol% or less, preferably 40 mol% or less. is there.

On a mass basis, the polyhydric alcohol is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the polyhydric alcohol, the polybasic acid, the unsaturated fatty acid and / or the fat and oil. For example, it is 40 parts by mass or less, preferably 30 parts by mass or less. The polybasic acid is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass or less. The amount of unsaturated fatty acids and / or fats and oils (total amount) is, for example, 30 parts by mass or more, preferably 40 parts by mass or more, and for example, 70 parts by mass or less, preferably 60 parts by mass or less.

In the condensation reaction (and transesterification reaction), a solvent (for example, xylene, toluene, methyl isobutyl ketone, a weak solvent described later, etc.) or a known catalyst should be added at an appropriate ratio, if necessary. Can be done. Further, after the reaction is completed, the solvent and the catalyst can be removed by a known method.

As a result, unsaturated fatty acid residues (including unsaturated fatty acid residues in fats and oils when fats and oils are used) are introduced into the molecules of the alkyd resin, and as a result, an alkyd resin having an oxidatively polymerizable group is obtained. Be done.

The ratio of unsaturated fatty acids and fats and oils in the alkyd resin (hereinafter referred to as oil length) is, for example, 10% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, for example, 90%. It is mass% or less, preferably 70 mass% or less, and more preferably 60 mass% or less.

The oil length is the mass ratio of unsaturated fatty acids and fats and oils (further, saturated fatty acids to be blended if necessary) in the raw material of the alkyd resin, and is calculated by the following formula.

Oil length (mass%) = (mass of fatty acid or fat / total mass of alkyd resin raw material) x 100
When the oil length is within the above range, when the obtained paint resin is used as a paint base resin, a coating film having excellent oxidative curability and excellent crosslink density, initial gloss, weather resistance and initial drying property can be obtained. Be done.

Further, when the oil length is within the above range, hydrocarbon groups derived from unsaturated fatty acids and fats and oils are appropriately introduced into the molecules of the alkyd resin, so that the dilution property with a weak solvent (solubility in a solvent) is excellent. ..

The acid value of the alkyd resin is, for example, 3.5 mgKOH / g or more, preferably 6.5 mgKOH / g or more, and for example, 16.0 mgKOH / g or less, preferably 12.5 mgKOH / g or less. ..

The acid value is measured in accordance with JIS K 5601-2-1 (1999) (the same applies hereinafter).

Further, the alkyd resin can be prepared as a solution or a dispersion by dissolving or dispersing it in a solvent (such as a weak solvent described later), if necessary.

In such a case, the non-volatile content concentration in the solution or dispersion of the alkyd resin is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less. is there.

The acid value of the alkyd resin solution or dispersion (solid content 60% by mass) is, for example, 3.5 mgKOH / g or more, preferably 6.5 mgKOH / g or more, and for example, 16.0 mgKOH / g or less, preferably 16.0 mgKOH / g or less. Is 12.5 mgKOH / g or less.

The polymerizable monomer component is a monomer that can be graft-polymerized with respect to the above-mentioned alkyd resin, and examples thereof include a monomer having an ethylenically unsaturated group.

Specifically, the polymerizable monomer component includes (A) a ring structure-containing (meth) acrylate, (B) an alkyl (meth) acrylate having an alkyl group having 10 to 35 carbon atoms, and (C) styrenes. (D) Contains at least one carboxyl group-terminated-monofunctional (meth) acrylic compound represented by (d1) to (d3) described later.

The (meth) acrylate is defined as acrylate and / or methacrylate, and the (meth) acrylic is defined as acrylic and / or methacrylic.

The (A) ring structure-containing (meth) acrylate is a (meth) acrylate having one or more ring structures.

Ring structures include alicyclics and / or aromatic rings.

The alicyclic has a structure in which carbon-containing elements are cyclically bonded and does not have aromaticity (described later). A structure in which carbon is cyclically bonded and a single or multiple heteroatoms are contained in a structure having no aromaticity (complex alicyclic) is included in the alicyclic.

The aromatic ring is a structure in which an element containing carbon is cyclically bonded and has an aromatic property. Aromaticity means a ring having a (4n + 2) π electron system (n is a natural number).

A structure in which carbon is cyclically bonded and a single or a plurality of heteroatoms are contained in a structure having aromaticity (heteroaromatic ring) is included in the aromatic ring.

Examples of the ring structure-containing (meth) acrylate include a (meth) acrylate having one alicyclic ring, a (meth) acrylate having two or more alicyclic rings, and a (meth) acrylate having one aromatic ring. Examples thereof include (meth) acrylates having two or more aromatic rings.

Examples of the (meth) acrylate having one alicyclic include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth) acrylate. Meta) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, n-butylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dimethylcyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, cyclic trimethylolpropanformal (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3) Examples thereof include (meth) acrylate having a saturated alicyclic group consisting of one ring such as −yl) methyl (meth) acrylate.

Examples of the (meth) acrylate having two or more alicyclics include isobornyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, and dimethyl adamantyl (meth). Acrylate, bicyclo [4.4.0] decanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclopentanyl (meth) acrylate, tricyclopentenyl (meth) acrylate, Examples thereof include (meth) acrylate having a saturated alicyclic group consisting of two or more rings such as tricyclodecanyl (meth) acrylate and dicyclopentanyloxyethyl (meth) acrylate.

Examples of the (meth) acrylate having one aromatic ring include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate. , Phenoxypolypropylene glycol (meth) acrylate and the like.

Examples of the (meth) acrylate having two or more aromatic rings include biphenyl (meth) acrylate and ethoxylated ortho-phenylphenol (meth) acrylate.

These (A) ring structure-containing (meth) acrylates can be used alone or in combination of two or more.

Examples of the (A) ring structure-containing (meth) acrylate include (meth) acrylate having two or more alicyclic rings, and more preferably isobornyl (meth) acrylate.

As the (B) alkyl (meth) acrylate, an alkyl (meth) acrylate having an alkyl group having 10 to 35 carbon atoms (hereinafter, referred to as C10 to 35 alkyl (meth) acrylate) is used.

Specific examples of the C10 to 35 alkyl (meth) acrylate include decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and 1-methyl. Linear or branched such as tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eikosyl (meth) acrylate, docosyl (meth) acrylate, tetracosyl (meth) acrylate, and triacontyl (meth) acrylate. Examples thereof include alkyl (meth) acrylates having an alkyl group having 10 to 35 carbon atoms.

These (B) C10 to 35 alkyl (meth) acrylates can be used alone or in combination of two or more.

(B) Examples of the C10 to 35 alkyl (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, and more preferably an alkyl having an alkyl group having 11 to 15 carbon atoms. Examples thereof include (meth) acrylates, and particularly preferably alkyl (meth) acrylates having an alkyl group having 12 to 14 carbon atoms. Specific examples thereof include dodecyl (meth) acrylate, tridecylic (meth) acrylate and tetradecyl (meth) acrylate, and more preferably dodecyl (meth) acrylate and tetradecyl (meth) acrylate.

(C) Styrene is styrene and its derivatives, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene and the like. Can be mentioned.

These (C) styrenes can be used alone or in combination of two or more.

As the styrenes (C), styrene is preferably mentioned.

Examples of the (D) carboxyl group-terminated-monofunctional (meth) acrylic compound include the compounds represented by the following (d1) to (d3).

(D1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).

CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1)
(In the formula (1), R ¹ represents a hydrogen atom and a methyl group, and n represents 1 to 10).
(D2) An acid anhydride modified product of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).

CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2)
(In the formula (2), R ¹ represents a hydrogen atom and a methyl group, R ² represents at least one selected from the group consisting of an ethylene group, a propylene group and a tetramethylene group, and n represents 1 to 1. 10 is shown.)
(D3) An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).

CH ₂ = C (R ¹ ) COO ( _Cm H _2m O) _n H (3)
(In the formula (3), R1 represents a hydrogen atom and a methyl group, m represents 2 to 4, and n represents 1 to 10.)
In the following, each of the compounds represented by the above (d1) to (d3) will be described in detail.

The compound represented by (d1) is a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).

CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1)
(In the formula (1), R ¹ represents a hydrogen atom and a methyl group, and n represents 1 to 10).
In the above formula (1), R ¹ represents a hydrogen atom and / or a methyl group, and preferably represents a hydrogen atom.

Further, in the above formula (1), n is the average number of moles of caprolactone added to 1 mol of (meth) acrylic acid, which is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. Preferably, it is 3 or less.

Such a caprolactone adduct of (meth) acrylic acid can be obtained by subjecting (meth) acrylic acid to an addition reaction (ring-opening addition) of ε-caprolactone.

The (meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.

The ε-caprolactone is not particularly limited, and a commercially available product can be used as it is.

The method for reacting (meth) acrylic acid with ε-caprolactone (ring-opening addition) is not particularly limited, and is described in known methods (for example, JP-A-62-135521, JP-A-60-67446, etc.). Method) can be adopted.

The caprolactone adduct of (meth) acrylic acid can also be obtained, for example, by an esterification reaction (condensation polymerization) of (meth) acrylic acid and ω-hydroxycaproic acid in which caprolactone is ring-opened.

(D1) Specific examples of the caprolactone adduct of (meth) acrylic acid include, for example, ω-carboxy-monocaprolactone mono (meth) acrylate, ω-carboxy-dicaprolactone mono (meth) acrylate, and ω-carboxy-tri. Included are ω-carboxy-polycaprolactone (meth) acrylates such as caprolactone (monometh) acrylate, ω-carboxy-tetracaprolactone mono (meth) acrylate, and ω-carboxy-pentacaprolactone mono (meth) acrylate. These can be used alone or in combination of two or more.

The caprolactone adduct of (meth) acrylic acid can also be obtained as a commercial product. Examples of such a commercially available product include Aronix M-5300 (ω-carboxy-polycaprolactone monoacrylate, manufactured by Toagosei).

(D1) The acid value of the caprolactone adduct of (meth) acrylic acid represented by the above formula (1) is, for example, 45 mgKOH / g or more, preferably 135 mgKOH / g or more, and for example, 310 mgKOH / g or less. ..

The compound represented by (d2) is an acid anhydride modified product of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).

CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2)
(In the formula (2), R ¹ represents a hydrogen atom and a methyl group, R ² represents at least one selected from the group consisting of an ethylene group, a propylene group and a tetramethylene group, and n represents 1 to 1. 10 is shown.)
In the above formula (2), R ¹ represents a hydrogen atom and / or a methyl group, and preferably represents a hydrogen atom.

Further, in the above formula (2), R ² represents at least one selected from the group consisting of an ethylene group, a propylene group and a tetramethylene group, and preferably represents an ethylene group.

Further, in the above formula (2), n is the average number of moles of caprolactone added to 1 mol of hydroxyalkyl (meth) acrylate, which is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. is there.

To obtain the compound represented by (d2), for example, first, hydroxyalkyl (meth) acrylate is reacted (ring-opened adduct) with ε-caprolactone, and then hydroxyalkyl (meth) acrylate represented by the above formula (2) is obtained. To obtain the caprolactone adduct of. Then, the caprolactone adduct of the hydroxyalkyl (meth) acrylate represented by the above formula (2) is reacted with the acid anhydride.

Examples of the hydroxyalkyl (meth) acrylate include hydroxyalkyl (meth) acrylates having a hydroxyalkyl group having 2 to 4 carbon atoms, and specific examples thereof include 2-hydroxyethyl (meth) acrylate and 3-hydroxy. Examples thereof include propyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

These hydroxyalkyl (meth) acrylates can be used alone or in combination of two or more.

As the hydroxyalkyl (meth) acrylate, preferably, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 carbon atoms can be mentioned, and more preferably, 2-hydroxyethyl (meth) acrylate can be mentioned.

The ε-caprolactone is not particularly limited, and a commercially available product can be used as it is.

The method for reacting (ring-opening addition) the hydroxyalkyl (meth) acrylate with ε-caprolactone is not particularly limited, and a known method (for example, the method described in JP-A-10-7774) is adopted. Can be done.

The caprolactone adduct of hydroxyalkyl (meth) acrylate can also be obtained as a commercially available product. Examples of such commercially available products include Praxel FA-1, Praxel FA-2, Praxel FA-2D, Praxel FA-3, Praxel FA-4, Praxel FA-5, Praxel FA-10L, and Praxel FM-1. Examples thereof include PLAXEL FM-2, PLAXEL FM-2D, PLAXEL FM-3, PLAXEL FM-4, and PLAXEL FM-5 (all manufactured by Daicel Chemical Co., Ltd.) (PLACCEL is a registered trademark).

These hydroxyalkyl (meth) acrylate caprolactone adducts can be used alone or in combination of two or more.

Then, by reacting the above-mentioned caprolactone adduct of hydroxyalkyl (meth) acrylate with an acid anhydride, it is shown by an acid anhydride modified product of the caprolactone adduct of hydroxyalkyl (meth) acrylate (that is, (d2)). Compound) can be obtained.

Examples of the acid anhydride include dicarboxylic acid monoanhydride, tricarboxylic acid monoanhydride, and tetracarboxylic dianhydride.

Examples of the dicarboxylic acid monoanhydride include succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (C12 to C18) succinic anhydride, tetrahydrophthalic anhydride, hymic acid anhydride, and hexahydro. Examples thereof include phthalic anhydride, tetrabromophthalic anhydride, and tetrachlorophthalic anhydride.

Examples of the tricarboxylic acid monoanhydride include trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and the like.

Examples of the tetracarboxylic dianhydride include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2,5-oxotetrahydrofuryl). Examples thereof include -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride.

These acid anhydrides can be used alone or in combination of two or more.

Examples of the acid anhydride include dicarboxylic acid monoanhydride, more preferably succinic anhydride and phthalic anhydride, and further preferably succinic anhydride, from the viewpoint of coating film hardness.

Then, in the reaction between the caprolactone adduct of hydroxyalkyl (meth) acrylate and the acid anhydride, for example, the caprolactone adduct of hydroxyalkyl (meth) acrylate and the acid anhydride are blended in a predetermined ratio, and if necessary. , A known solvent, a known catalyst, etc. are used for heating.

The mixing ratio of the caprolactone adduct of hydroxyalkyl (meth) acrylate to the acid anhydride is, for example, the equivalent ratio of the hydroxyl group in the caprolactone adduct of hydroxyalkyl (meth) acrylate to the carboxylic acid anhydride in the acid anhydride. The (carboxylic acid anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, and for example, 1 or less, preferably 0.91 or less.

As reaction conditions, the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, preferably 140 ° C. or lower, in an atmosphere of an oxygen gas or an inert gas-oxygen gas mixture. Is 110 ° C. or lower. The heating time is, for example, 4 hours or more, preferably 8 hours or more, and for example, 20 hours or less, preferably 12 hours or less.

As a result, an acid anhydride modified product of the caprolactone adduct of the hydroxyalkyl (meth) acrylate (that is, the compound represented by (d2)) is obtained.

(D2) The acid value of the acid anhydride modified product of the caprolactone adduct of the hydroxyalkyl (meth) acrylate represented by the above formula (2) is, for example, 40 mgKOH / g or more, preferably 60 mgKOH / g or more, for example. 280 mgKOH / g or less, preferably 150 mgKOH / g or less.

The compound represented by (d3) is an acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3).

CH ₂ = C (R ¹ ) COO ( _Cm H _2m O) _n H (3)
(In the formula (3), R1 represents a hydrogen atom and a methyl group, m represents 2 to 4, and n represents 1 to 10.)
In the above formula (3), R ¹ represents a hydrogen atom and / or a methyl group, and preferably represents a hydrogen atom.

Further, in the above formula (3), m is 2 or more, 4 or less, preferably 3 or less.

That is, the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) has an oxyalkylene ( _Cm H 2m O) having _{2 to 4 carbon atoms.}

Examples of oxyalkylene having 2 to 4 carbon atoms include oxyethylene (-CH ₂ CH ₂ O-), oxytrimethylene (-CH ₂ CH ₂ CH ₂ O-), and oxytetramethylene (-CH ₂ CH ₂ CH ₂ CH). _{Linear oxyalkylenes such as 2} O-), such as oxypropylene (-CH ₂ CH (CH ₃ ) O-), oxybutylene (-CH ₂ CH (CH ₂ CH ₃ ) O-, -CH (CH ₃₎ ) CH (CH ₃ ) O−) and the like, such as branched oxyalkylene, preferably linear oxyalkylene, and more preferably oxyethylene.

Further, in the above formula (3), n is the average number of moles of alkylene oxide added to 1 mol of (meth) acrylic acid, which is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. is there.

To obtain the compound represented by (d3), for example, first, (meth) acrylic acid and alkylene oxide are reacted (cycloaddition), and the alkylene of (meth) acrylic acid represented by the above formula (3) is obtained. Obtain an oxide adduct. Then, the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is reacted with the acid anhydride.

The (meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.

Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms, and specific examples thereof include cyclic ether compounds having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, trimethylene oxide (oxetane), and butylene oxide. Be done.

These alkylene oxides can be used alone or in combination of two or more.

When two or more types of alkylene oxides are used in combination, the addition form thereof is not particularly limited, and may be, for example, random addition or block addition.

Examples of the alkylene oxide are preferably ethylene oxide and propylene oxide, and more preferably ethylene oxide.

The method for adding the alkylene oxide to (meth) acrylic acid is not particularly limited, and a known method can be adopted.

More specifically, as an alkylene oxide adduct of (meth) acrylic acid, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polybutylene glycol mono (meth). ) Acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) ) Hydroxyl terminal polyalkylene glycol mono (meth) acrylate such as mono (meth) acrylate, for example, (mono) ethylene glycol mono (meth) acrylate, (mono) propylene glycol mono (meth) acrylate, (mono) trimethylene glycol mono Examples thereof include hydroxyl group-terminated monoalkylene glycol mono (meth) acrylates such as (meth) acrylates, (mono) butylene glycol mono (meth) acrylates, and (mono) tetramethylene glycol mono (meth) acrylates.

These (meth) acrylic acid alkylene oxide adducts can be used alone or in combination of two or more.

The alkylene oxide adduct of (meth) acrylic acid is preferably a hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate, and more preferably polyethylene glycol mono (meth) acrylate.

The alkylene oxide adduct of (meth) acrylic acid can also be obtained as a commercially available product. Examples of such commercially available products include the Blemmer PE series, the Blemmer AE series, the Blemmer PP series, the Blemmer AP series, the Blemmer PEP series, the Blemmer AEP series, the Blemmer PET series, the Blemmer AET series, the Blemmer PPT series, and the Blemmer APT series ( All of them are made by NOF Corporation). These can be used alone or in combination of two or more.

Then, by reacting the above-mentioned alkylene oxide adduct of (meth) acrylic acid with an acid anhydride, it is shown by an acid anhydride modified product of the alkylene oxide adduct of (meth) acrylic acid (that is, (d3)). Compound) can be obtained.

Examples of the acid anhydride include the above-mentioned acid anhydrides, preferably dicarboxylic acid monoanhydrides, and more preferably succinic anhydride and phthalic anhydride from the viewpoint of the hardness of the cured product (described later). And more preferably, succinic anhydride.

Then, in the reaction between the alkylene oxide adduct of (meth) acrylic acid and the acid anhydride, for example, the alkylene oxide adduct of (meth) acrylic acid and the acid anhydride are blended in a predetermined ratio, and if necessary. , A known solvent, a known catalyst, etc., for heating.

The mixing ratio of the caprolactone additive of the alkylene oxide adduct of (meth) acrylic acid and the acid anhydride is, for example, the carboxylic acid anhydride group in the acid anhydride with respect to the hydroxyl group in the alkylene oxide adduct of (meth) acrylic acid. The equivalent ratio with and (carboxylic acid anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, and for example, 1 or less, preferably 0.91 or less.

As reaction conditions, the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower under an oxygen atmosphere or an inert gas-oxygen gas mixture atmosphere. Preferably, it is 110 ° C. or lower. The heating time is, for example, 4 hours or more, preferably 8 hours or more, and for example, 20 hours or less, preferably 12 hours or less.

As a result, an acid anhydride modified product of the alkylene oxide adduct of (meth) acrylic acid (that is, the compound represented by (d3)) is obtained.

(D3) The acid value of the acid anhydride modified product of the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is, for example, 55 mgKOH / g or more, preferably 95 mgKOH / g or more, for example. , 400 mgKOH / g or less, preferably 300 mgKOH / g or less.

These (D) carboxyl group-terminated-monofunctional (meth) acrylic compounds can be used alone or in combination of two or more.

Such (D) a carboxyl group-terminated - the monofunctional (meth) acrylic compound, a non-polar groups to improve the dilution properties for weak solvent (formula (1) and (2) in the (CH _{2) 5,} wherein ( and 3) in the _(such as _{C m H 2m O) n)} , are having both a polar group to improve the compatibility with other resins (such as C = O group).

Therefore, by using the (D) carboxyl group terminal-monofunctional (meth) acrylic compound, it is possible to obtain a coating resin having both dilutability with a weak solvent and compatibility with other resins.

From the viewpoint of dispersibility, the (D) carboxyl group-terminated-monofunctional (meth) acrylic compound is preferably (d1) a caprolactone adduct of (meth) acrylic acid represented by the above formula (1).

In addition to the above (A) to (D), the polymerizable monomer component is a polymerizable monomer copolymerizable with the above (A) to (D) as an optional component (hereinafter, (E) and other polymerizable monomers. ) Can be included.

Examples of the other polymerizable monomer include a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer (however, (D) carboxyl group-terminated-monofunctional (where shown in (d1) to (d3) above). Meta) Acrylic compounds are excluded (the same applies hereinafter)), and examples thereof include a tertiary amino group-containing polymerizable monomer and a quaternary ammonium group-containing polymerizable monomer.

Examples of the hydroxyl group-containing polymerizable monomer include a monomer having both a hydroxyl group and an ethylenically unsaturated group. Specific examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). ) Acrylate (also known as 2-hydroxypropyl (meth) acrylate), 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and other hydroxyl group-containing (meth) Examples include acrylate. These can be used alone or in combination of two or more. The hydroxyl group-containing polymerizable monomer is preferably a hydroxyl group-containing (meth) acrylate, and more preferably 2-hydroxypropyl (meth) acrylate.

Examples of the carboxyl group-containing polymerizable monomer include a monomer having both a carboxyl group and an ethylenically unsaturated group. Specific examples thereof include (meth) acrylic acid, itaconic acid, fumaric acid, and maleic acid. Α, β-unsaturated carboxylic acid of. Further, for example, a half esterified product of the above-mentioned hydroxyl group-containing alkyl (meth) acrylate and the above-mentioned acid anhydride can be mentioned. These can be used alone or in combination of two or more. The carboxyl group-containing polymerizable monomer is preferably α, β-unsaturated carboxylic acid, and more preferably (meth) acrylic acid.

Examples of the tertiary amino group-containing polymerizable monomer include a monomer having both a tertiary amino group and an ethylenically unsaturated group, and specifically, N, N-dimethylaminoethyl (meth) acrylate (also known as). (Dimethylaminoethyl (meth) acrylate), N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-di-t-butylaminoethyl (meth) acrylate, N , N, N-dialkylaminoalkyl (meth) acrylates such as N-dimethylaminobutyl (meth) acrylates, N, N-dimethylaminoethyl (meth) acrylamides, N, N-diethylaminoethyl (meth) acrylamides, N, N Examples thereof include N, N-dialkylaminoalkyl (meth) acrylamide such as −dimethylaminopropyl (meth) acrylamide. These can be used alone or in combination of two or more. The tertiary amino group-containing polymerizable monomer is preferably N, N-dialkylaminoalkyl (meth) acrylate, and more preferably N, N-diethylaminoethyl (meth) acrylate.

Examples of the quaternary ammonium group-containing polymerizable monomer include a monomer having both a quaternary ammonium group and an ethylenically unsaturated group, and specifically, quaternization with the above-mentioned tertiary amino group-containing polymerizable monomer. Examples thereof include a quaternary product obtained by reacting with an agent (epihalohydrin, benzyl halide, alkyl halide, etc.).

More specifically, as the quaternized product of the tertiary amino group-containing polymerizable monomer, for example, 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, 2-((meth) acryloyloxy) ethyltrimethylammonium bromide, 2-((Meta) acryloyloxyalkyltrialkylammonium salts such as (meth) acryloyloxy) ethyltrimethylammonium dimethyl phosphate, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium bromide and the like (meth) ) Acryloylaminoalkyltrialkylammonium salt and the like can be mentioned. These can be used alone or in combination of two or more.

Further, examples of the (E) other polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meta) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Examples thereof include alkyl (meth) acrylates having an alkyl group having 9 or less carbon atoms such as acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and nonyl (meth) acrylate.

Further, examples of the (E) other polymerizable monomer include (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl chloride, vinylpyrrolidone, vinyloxazoline, acryloylmorpholine and the like.

These (E) other polymerizable monomers can be used alone or in combination of two or more.

(E) As the other polymerizable monomer, preferably, a hydroxyl group-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, a tertiary amino group-containing polymerizable monomer, or a quaternary ammonium group-containing polymerizable monomer can be used alone or in combination. Be done.

(E) When a hydroxyl group-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, a tertiary amino group-containing polymerizable monomer, or a quaternary ammonium group-containing polymerizable monomer is used as the other polymerizable monomer, the charge on the surface of the pigment particles is used. Can be controlled, and the pigment dispersibility when the coating resin is used as the coating dispersant (pigment dispersant) is improved.

Further, as the (E) other polymerizable monomer, from the viewpoint of improving the pigment dispersibility, the hydroxyl group-containing polymerizable monomer, the carboxyl group-containing polymerizable monomer, the tertiary amino group-containing polymerizable monomer and / Alternatively, it may be used in combination with a quaternary ammonium group-containing polymerizable monomer.

In the polymerizable monomer component, the content ratio of each component is appropriately set as long as the excellent effect of the present invention is not impaired.

Specifically, the content ratio of (A) ring structure-containing (meth) acrylate is, for example, 20% by mass or more, preferably 22% by mass or more, and for example, 40, based on the total amount of the polymerizable monomer component. It is mass% or less, preferably 38 mass% or less.

Further, the molar concentration of the (A) ring structure-containing (meth) acrylate is, for example, 0.901 mol / kg or more, preferably 0.991 mol / kg or more, based on the total amount of the polymerizable monomer component. For example, it is 1.802 mol / kg or less, preferably 1.712 mol / kg or less.

(A) If the content ratio of the ring structure-containing (meth) acrylate is above the above lower limit, the dilution property with respect to a weak solvent can be improved, and if it is below the above upper limit, the weather resistance of the coating film is improved. Can be improved.

Further, the content ratio of (B) C10 to 35 alkyl (meth) acrylate is, for example, 10% by mass or more, preferably 12% by mass or more, and for example, 20% by mass, based on the total amount of the polymerizable monomer component. Hereinafter, it is preferably 18% by mass or less.

The molar concentration of (B) C10-35 alkyl (meth) acrylate is, for example, 0.380 mol / kg or more, preferably 0.456 mol / kg or more, based on the total amount of the polymerizable monomer component. For example, it is 0.760 mol / kg or less, preferably 0.684 mol / kg or less.

(B) If the content ratio of C10 to 35 alkyl (meth) acrylate exceeds the above lower limit, the dilution property with respect to a weak solvent can be improved, and if it is less than the above upper limit, the coating film is dried. It is possible to improve the sex.

The content ratio of (C) styrenes to the total amount of the polymerizable monomer component is, for example, 40% by mass or more, preferably 45% by mass or more, and for example, 60% by mass or less, preferably 55. It is less than mass%.

Further, the molar concentration of (C) styrenes is, for example, 3.846 mol / kg or more, preferably 4.327 mol / kg or more, and for example, 5.769 with respect to the total amount of the polymerizable monomer component. It is mol / kg or less, preferably 5.288 mol / kg or less.

(C) If the content ratio of styrenes is above the above lower limit, the glossiness of the coating film can be improved, and if it is below the above upper limit, the weather resistance of the coating film can be improved. Can be done.

Further, the content ratio of the (D) carboxyl group terminal-monofunctional (meth) acrylic compound to the total amount of the polymerizable monomer component is, for example, 0.2% by mass or more, preferably 0.5% by mass or more. Yes, for example, 4.5% by mass or less, preferably 3.0% by mass or less, more preferably 2.5% by mass or less.

Further, the molar concentration of the (D) carboxyl group terminal-monofunctional (meth) acrylic compound is, for example, 0.0067 mol / kg or more, preferably 0.017 mol / kg, based on the total amount of the polymerizable monomer component. The above is, for example, 0.15 mol / kg or less, preferably 0.1 mol / kg or less.

(D) If the content ratio of the carboxyl group terminal-monofunctional (meth) acrylic compound exceeds the above lower limit, the dilutability with respect to a weak solvent and the pigment dispersibility when used with a paint dispersant should be improved. If it is less than the above upper limit, the water resistance of the coating film can be improved.

When the polymerizable monomer component contains (E) other polymerizable monomer, the content ratio (total amount) of (E) the other polymerizable monomer is, for example, 1 with respect to the total amount of the polymerizable monomer component. By mass% or more, preferably 3% by mass or more, for example, 9% by mass or less, preferably 7% by mass or less.

In particular, when the polymerizable monomer component contains a carboxyl group-containing polymerizable monomer, the content ratio thereof is, for example, 0.05% by mass or more, preferably 0.08% by mass, based on the total amount of the polymerizable monomer component. % Or more, for example, 1.7% by mass or less, preferably 1.3% by mass or less.

If the content ratio of the carboxyl group-containing polymerizable monomer is above the above lower limit, the pigment dispersibility when used with a paint dispersant can be improved, and if it is below the above upper limit, the coating film Water resistance can be improved.

When the polymerizable monomer component contains a hydroxyl group-containing polymerizable monomer, the content ratio thereof is, for example, 1.0% by mass or more, preferably 3.0% by mass, based on the total amount of the polymerizable monomer component. % Or more, for example, 10% by mass or less, preferably 7.0% by mass or less.

If the content ratio of the hydroxyl group-containing polymerizable monomer is above the above lower limit, the pigment dispersibility when used with a paint dispersant can be improved, and if it is below the above upper limit, the coating film Water resistance can be improved.

When the polymerizable monomer component contains a tertiary amino group-containing polymerizable monomer and / or a quaternary ammonium group-containing polymerizable monomer, the content ratio thereof is, for example, 0 with respect to the total amount of the polymerizable monomer component. .3% by mass or more, preferably 0.6% by mass or more, for example, 2.5% by mass or less, preferably 1.2% by mass or less.

If the content ratio of the tertiary amino group-containing polymerizable monomer and / or the quaternary ammonium group-containing polymerizable monomer exceeds the above lower limit, the pigment dispersibility when used with a paint dispersant can be improved. Further, if it is less than the above upper limit, the water resistance of the coating film can be improved.

Then, the alkyd-acrylic resin can be obtained by graft-polymerizing the above-mentioned polymerizable monomer component on the alkyd resin.

The graft polymerization method is not particularly limited, and a known method can be adopted. Specifically, the alkyd resin and the polymerizable monomer component are mixed in an inert gas atmosphere such as nitrogen gas or argon gas, and heated (and, if necessary, irradiated with energy rays) to carry out graft polymerization.

The mixing ratio of the alkyd resin and the polymerizable monomer component is, for example, 0.5 parts by mass or more, preferably 1% by mass or more, and for example, 10 parts by mass of the alkyd resin with respect to 100 parts by mass of the polymerizable monomer component. It is less than or equal to parts by mass, preferably less than or less than 7.0 parts by mass.

When the ratio of the alkyd resin is within the above range, the compatibility with other resins can be improved.

In addition, a polymerization initiator can be blended together with the alkyd resin and the polymerizable monomer component, if necessary.

The polymerization initiator is not particularly limited, and is appropriately selected depending on the type of alkyd resin, the type of polymerizable monomer component, the reaction conditions, and the like. Specific examples of the polymerization initiator include radical polymerization initiators and photopolymerization initiators.

Examples of the radical polymerization initiator include azo compounds, peroxide compounds, sulfides, sulfines, sulfin acids, diazo compounds, resox compounds and the like, and azo compounds and peroxide compounds are preferable. Can be mentioned.

Examples of the azo compound include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), and dimethyl 2,2'-azo. Examples thereof include bisisobutyrate and 4,4'-azobis-4-cyanovaleric acid.

Examples of the peroxide compound include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, capriel peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, acetylcyclohexylsulfonyl peroxide, and t-butylper. Oxyviparate, t-butylperoxy-2-ethylhexanoate, 1,1-di-t-butylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane , 1,1-di-t-hexyl peroxy-3,3,5-trimethylcyclohexane, isopropyl peroxy dicarbonate, isobutyl peroxy dicarbonate, s-butyl peroxy dicarbonate, n-butyl peroxy dicarbonate, 2-Ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-amylperoxy-2-ethylhexaeneto, 1,1,3,3-tetramethylbutylperoxy-ethyl Hexanoate, 1,1,2-trimethylpropylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-amylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl carbonate , T-Butyl Peroxyallyl Carbonate, t-Butyl Peroxyisopropyl Carbonate, 1,1,3,3-Tetramethylbutylperoxyisopropyl Monocarbonate, 1,1,2-trimethylpropylperoxyisopropyl Monocarbonate, 1, 1,3,3-Tetramethylbutylperoxyisononaate, 1,1,2-trimethylpropylperoxy-isononaate, t-butylperoxybenzoate, t-hexylperoxyisopropylmonocarbonate, t-amylperoxy Examples thereof include organic peroxides such as -3,5,5-trimethylhexanoate.

These radical polymerization initiators can be used alone or in combination of two or more.

Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 1-cyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenyl. -Propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples thereof include fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone and the like.

These photopolymerization initiators can be used alone or in combination of two or more.

The polymerization initiator can be used alone or in combination of two or more. The polymerization initiator preferably includes a radical polymerization initiator, more preferably a peroxide-based compound, and further preferably 1,1,3,3-tetramethylbutylperoxy-ethylhexanoate. Can be mentioned.

The mixing ratio of the polymerization initiator is, for example, 1.5 parts by mass or more, preferably 3.0 parts by mass or more, and for example, 5.0 parts by mass or less, preferably 5.0 parts by mass or more, based on 100 parts by mass of the polymerizable monomer component. Is 4.0 parts by mass or less.

The method for blending the alkyd resin, the polymerizable monomer component and the polymerization initiator is not particularly limited, and for example, a method of dropping a mixture of the polymerizable monomer component and the polymerization initiator into a reaction vessel containing the alkyd resin, for example, alkyd. A method of dropping the rest of the polymerizable monomer component and the polymerization initiator into a reaction vessel containing a resin and a part of the polymerizable monomer component, for example, polymerization in a reaction vessel containing an alkyd resin and a polymerizable monomer component. A method of dropping the initiator, for example, a method of dropping the alkyd resin and the polymerization initiator into a reaction vessel containing the polymerizable monomer component, for example, a method of dropping the polymerizable monomer component and the polymerization initiator into a reaction vessel containing the alkyd resin. Examples thereof include a method in which the mixture with a part is added dropwise, and then the rest of the polymerization initiator is added dropwise after a while.

The reaction temperature is, for example, 50 to 150 ° C., and the reaction time is, for example, 3 to 20 hours.

As a result, the polymer ((meth) acrylic resin) of the polymerizable monomer component is graft-polymerized with the alkyd resin to obtain an alkyd-acrylic resin.

The alkyd-acrylic resin is an acrylic-modified alkyd resin (alkyd-modified alkyd resin) and / or an alkyd-modified acrylic resin (alkyd-modified acrylic resin).

More specifically, in the above reaction, the polymer (acrylic resin) of the polymerizable monomer component is graft-added to the alkyd resin, so that the reaction product is modified with the alkyd resin (that is, the acrylic resin). Acrylic modified alkyd resin) may be referred to.

When the reaction product contains a polymer (acrylic resin) as a polymerizable monomer component as a main component, the reaction product is referred to as an acrylic resin modified with an alkyd resin (that is, an alkyd-modified acrylic resin). In some cases.

In the alkyd-acrylic resin, the polymerizable monomer component is usually graft-added to the alkyd resin as a polymer (acrylic resin), but if necessary, the polymerizable monomer component can be added to the alkyd resin as a monomer. On the other hand, a graft may be added.

The weight average molecular weight (GPC measurement: polystyrene conversion) of the obtained alkyd-acrylic resin is, for example, 10,000 or more, preferably 20,000 or more, for example, 50,000 or less, preferably 40,000 or less. Is.

A paint resin containing such an alkyd-acrylic resin can have both dilutability with a weak solvent and compatibility with other resins.

Specifically, in this paint resin, the polymerizable monomer component that can be graft-polymerized with respect to the alkyd resin is the (D) carboxyl group-terminated-monofunctional (meth) acrylic compound represented by the above (d1) to (d3). Contains. Then, the (D) carboxyl group-terminated-monofunctional (meth) acrylic compound is a non-polar group (CH _{2 ) 5 in} the formula (1) and the formula (2), which improves the dilution property with respect to a weak solvent, and the formula (3). ) In ( _Cm H _2m O) _n, etc.) and a polar group (C = O group, etc.) that improves compatibility with other resins. Therefore, the paint resin can have both dilutability with a weak solvent and compatibility with other resins.

Therefore, it can be suitably used as a paint-based resin, a paint dispersant (pigment dispersant), or the like in a paint composition containing a weak solvent.

That is, the paint composition contains a weak solvent, a paint-based resin, a pigment, a paint dispersant (pigment dispersant), and the like. By containing the above-mentioned paint resin in a ratio of a predetermined amount or more described later with respect to the total amount of such a paint composition, the paint resin can act as a paint-based resin. Further, the paint resin can act as a paint dispersant (pigment dispersant) by containing the above-mentioned paint resin in a ratio of less than a predetermined amount, which will be described later, with respect to the total amount of the paint composition.

More specifically, when the above-mentioned paint resin is used as a paint dispersant (pigment dispersant), the paint composition comprises a base resin different from the above-mentioned paint resin, a weak solvent, a pigment, and a paint dispersion. Contains an agent (pigment dispersant).

Examples of the base resin include alkyd resin (long oil alkyd resin, etc.), rosinphenol resin, rosin ester resin, terpenphenol resin, kumaron inden resin, petroleum resin, and alkyd-modified acrylic resin (excluding the above-mentioned alkyd-acrylic resin). ), Silicone acrylic resin, modified silicone acrylic resin (alkyd modified silicone acrylic resin, etc.), epoxy resin, modified epoxy resin (Novolak modified epoxy resin), polyester resin, vinyl acetate resin, ethylene-vinyl acetate resin, urethane resin, urea Examples thereof include known base resins such as resins, melamine resins, and cellulose resins. These can be used alone or in combination of two or more.

The base resin is preferably an alkyd resin (long oil alkyd resin).

The content ratio (solid content) of the base resin is, for example, 15% by mass or more, preferably 25% by mass or more, and for example, 55% by mass or less, preferably 45% by mass, based on the total amount of the coating composition. It is as follows.

Examples of the weak solvent include aliphatic hydrocarbon solvents that may contain high boiling aromatic hydrocarbon solvents, and specifically, petroleum hydrocarbons such as mineral tarpen and mineral spirit. It shows a solvent with high flammability, high boiling point, and low toxicity.

Weak solvents are generally more environmentally friendly than strong solvents (solvents mainly composed of aromatic hydrocarbons such as toluene and xylene, ester solvents such as ethyl acetate, and ketone solvents such as methyl isobutyl ketone). It has little effect, low toxicity, and low odor.

On the other hand, since the weak solvent has low polarity, it is generally inferior in dilutability and compatibility with the coating resin.

Examples of such a weak solvent include paraffin-based solvents, naphthenic solvents, vegetable oil-based solvents, and the like.

Specifically, examples of the weak solvent include mixed solvents such as mineral spirit, white spirit, mineral tarpen, isoparaffin, solvent kerosene, aromatic naphtha, VM & P naphtha, and solvent naphtha.

Further, as a weak solvent, for example, aliphatic hydrocarbons such as n-butane, n-hexane, n-heptane, n-octane, isononan, n-decane, n-dodecane, cyclopentane, cyclohexane, cyclobutane, and methylcyclohexane. Single component solvents such as.

These weak solvents can be used alone or in combination of two or more.

As the weak solvent, a mixed solvent is preferably used, and a mineral spirit is more preferable.

The content ratio of the weak solvent is, for example, 20% by mass or more, preferably 30% by mass or more, and for example, 60% by mass or less, preferably 50% by mass or less, based on the total amount of the coating composition.

Examples of the pigment include known pigments such as carbon black, titanium oxide, calcium carbonate, iron oxide, barium sulfate, silica, clay, talc, quinacridone pigment, azo pigment, nitroso pigment, and phthalocyanine pigment. .. These pigments can be used alone or in combination of two or more.

The content ratio of the pigment is, for example, 10% by mass or more, preferably 15% by mass or more, and for example, 40% by mass or less, preferably 30% by mass or less, based on the total amount of the coating composition.

As the paint dispersant (pigment dispersant), the above-mentioned paint resin is used.

The content ratio (solid content) of the paint dispersant (pigment dispersant) is, for example, 0.05% by mass or more, preferably 0.10% by mass or more, and for example, 0, based on the total amount of the coating composition. It is less than .70% by mass, preferably 0.50% by mass or less.

As will be described in detail later, the paint resin of the present invention can be used as the base resin of the paint composition, but when the paint resin of the present invention is used as the paint dispersant (pigment dispersant), it is preferable. , The paint resin of the present invention is not used as the base resin, but other resins are used as the base resin.

In such a case, the content ratio (solid content) of the paint dispersant (pigment dispersant) is, for example, 0.1 mass by mass with respect to the base resin (resin different from the paint resin of the present invention) (solid content). % Or more, preferably 0.2% by mass or more, more preferably 0.4% by mass or more, for example, 1.4% by mass or less, preferably 1.2% by mass or less.

When the paint resin of the present invention is used as a paint dispersant, the paint dispersant exhibits excellent dispersibility even when the amount added to the base resin made of a resin different from the paint resin of the present invention is small. can do.

In particular, when the content ratio (solid content) of the paint dispersant (pigment dispersant) is 0.1% by mass or more with respect to the base resin, excellent dispersibility can be exhibited.

On the other hand, even if the content ratio (solid content) of the paint dispersant (pigment dispersant) is less than 0.1% by mass with respect to the base resin, the pigment can be dispersed. Further, by reducing the amount of the pigment dispersant added, it is possible to prevent the pigment dispersant from affecting the physical properties of the coating film of the base resin.

In addition, the coating composition can contain additives, if desired. Examples of the additive include known additives such as a desiccant (dryer), an antioxidant, a rust preventive, a plasticizer, a coating film surface conditioner, an antioxidant, an ultraviolet absorber, and a surfactant. .. These can be used alone or in combination of two or more.

The content ratio of the additive is appropriately set according to the purpose and application as long as the excellent effect of the present invention is not impaired.

Then, by mixing the above-mentioned base resin, weak solvent, pigment and paint dispersant (pigment dispersant) by a known method, a paint composition containing the above-mentioned paint resin as a paint dispersant (pigment dispersant) can be obtained. Obtainable.

Such a paint dispersant (pigment dispersant) and a paint composition contain an alkyd-acrylic resin in which a polymerizable monomer component is polymerized with respect to an alkyd resin, and the graft-polymerizable polymerizable monomer component thereof is contained. However, since it contains the above components (A) to (D), it can have both dilutability with a weak solvent and compatibility with other resins.

Further, since this paint dispersant contains the above-mentioned paint resin, it is excellent in pigment dispersibility.

When the above-mentioned paint resin is used as the paint-based resin, the paint composition contains the above-mentioned paint resin (paint-based resin), a weak solvent, and a pigment.

The content ratio (solid content) of the above-mentioned paint resin (paint base resin) is, for example, 15% by mass or more, preferably 25% by mass or more, and for example, 55% by mass or less, based on the total amount of the coating composition. , Preferably 45% by mass or less.

Further, the coating composition may contain a base resin other than the above-mentioned coating resin (hereinafter, referred to as a base resin other than the coating resin), if necessary. The content ratio of the base resin other than the paint resin is appropriately set according to the purpose and application as long as the excellent effect of the present invention is not impaired.

Examples of the weak solvent include the above-mentioned weak solvent. Further, the content ratio is, for example, 20% by mass or more, preferably 30% by mass or more, and for example, 60% by mass or less, preferably 50% by mass, based on the total amount of the coating composition, as described above. It is as follows.

Examples of the pigment include the above-mentioned pigments. Further, the content ratio is, for example, 10% by mass or more, preferably 15% by mass or more, and for example, 40% by mass or less, preferably 30% by mass, based on the total amount of the coating composition, as described above. It is as follows.

In addition, the coating composition can contain additives, if desired. Examples of the additive include a paint dispersant (pigment dispersant (excluding the above paint resin), a desiccant, a rust preventive, a plasticizer, a coating surface conditioner, an antioxidant, an ultraviolet absorber, and a surfactant. Known additives such as agents can be mentioned. These can be used alone or in combination of two or more.

The content ratio of the additive is appropriately set according to the purpose and application as long as the excellent effect of the present invention is not impaired.

Then, the above-mentioned paint resin (paint-based resin), a weak solvent and a pigment (further, a base resin other than the paint resin and an additive) are mixed by a known method to contain the above-mentioned paint resin as a paint-based resin. A coating composition can be obtained.

Such a paint-based resin and a paint composition contain an alkyd-acrylic resin in which a polymerizable monomer component is polymerized with respect to an alkyd resin, and the graft-polymerizable polymerizable monomer component thereof is the above (A). )-(D) are contained, so that it can have both dilutability with a weak solvent and compatibility with other resins.

Further, since this paint-based resin contains the above-mentioned paint resin, it is possible to obtain a coating film having excellent drying properties and excellent weather resistance.

The method for producing the coating film is not particularly limited, and the coating composition is applied to the object to be coated by a known method and dried.

The coating method is not particularly limited, and for example, coating using commonly used equipment such as a roll coater, a bar coater, a doctor blade, a Mayer bar, and an air knife, screen printing, and offset printing. , Flexographic printing, brush coating, spray coating, gravure coating, reverse gravure coating, and other known coating methods are adopted.

As the drying conditions, the drying temperature is, for example, 10 ° C. or higher, preferably 20 ° C. or higher, and for example, 50 ° C. or lower, preferably 40 ° C. or lower. The drying time is, for example, 12 hours or more, preferably 24 hours or more.

Thereby, the coating composition can be cured. As a result, a coating film is obtained as a cured product of the coating composition.

Such a coating film is obtained by curing a coating composition having both dilutability with a weak solvent and compatibility with other resins, and thus is excellent in productivity, uniformity (pigment dispersibility), and drying. It has excellent properties such as properties, weather resistance, and water resistance.

Therefore, the coating film is preferably used in the fields of, for example, iron and wood parts of buildings, intermediate coatings and top coatings of steel structures.

Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention" (forms for carrying out the invention). Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to.

Example 1
<Synthesis of alkyd resin>
The raw materials shown in Table 1 and 96 parts by mass of xylene as a reflux solvent were charged in a reaction vessel, the temperature was raised to 240 ° C., and the acid value was 20 mgKOH / g or less while removing water in the reaction system with a water separator. The mixture was reacted until it became a xylene solution of an alkyd resin (oil length 55.7%).

Then, when the acid value of the xylene solution of the alkyd resin became 20 mgKOH / g or less, xylene was removed by vacuum distillation and allowed to cool. Then, the obtained alkyd resin was diluted with 2037 parts by mass of mineral spirit (LAWS; manufactured by Shell Chemicals Japan (the same applies hereinafter)) to obtain a mineral spirit solution of alkyd resin having a non-volatile content (solid content) of 60.0% by mass. ..

The acid value of the obtained alkyd resin mineral spirit solution (solid content 60% by mass) was 9.5 mgKOH / g.

<Synthesis of alkyd-acrylic resin>
13.7 parts by mass (that is, 8.22 parts by mass of alkyd resin) of the mineral spirit solution (nonvolatile content 60.0% by mass) of the alkyd resin obtained above and 138.2 parts by mass of mineral spirit were placed in a reaction vessel. The temperature was raised to 120 ° C. with stirring while agitating the charged nitrogen gas.

Then, while maintaining 120 ° C., a mixture of the polymerizable monomer component shown in Table 2 and 7.06 parts by mass of 1,1,3,3-tetramethylbutylperoxy-ethylhexanoate as a polymerization initiator. Was added dropwise to the reaction vessel over 2 hours.

Then, after the completion of dropping the mixture, the mixture was aged at 120 ° C. for 4 hours to obtain an alkyd-acrylic resin (paint resin).

Then, the mixture was cooled to 80 ° C., and 36.8 parts by mass of mineral spirit was added to the reaction vessel to obtain a brown transparent and viscous alkyd-acrylic resin solution (nonvolatile content: 56.0% by mass).

The weight average molecular weight of the obtained alkyd-acrylic resin was measured by gel permeation chromatography (GPC).

Specifically, the sample was dissolved in tetrahydrofuran (concentration 1.0 g / L), measured by a GPC equipped with a differential refractometer (RID), and then standard polystyrene was obtained from the obtained chromatogram (chart). Was used as a calibration curve, and the weight average molecular weight (Mw) of the resin was calculated. The weight average molecular weight of the obtained resin was 31,300. The measuring device and measuring conditions are as follows.

Data processing device: HLC-8220GPC (manufactured by Tosoh)
Differential refractive index detector: RI detector built into HLC-8220GPC Column: TSKgel SuperHZM-H (manufactured by Tosoh) 2 mobile phase: tetrahydrofuran Column flow rate: 0.35 mL / min Sample concentration: 1.0 g / L
Injection volume: 10 μL
Measurement temperature: 40 ° C
Molecular weight marker: Standard polystyrene (standard material manufactured by POLYMER LABORATORIES) (using POLYSTYRENE-MEMDIUM MOLECULAR WEIGHT CALIBRATION KIT)

The details of the abbreviations in Table 2 are shown below.

N-Gerve CM-275: Alkyl methacrylate, mixture of C12 alkyl methacrylate and C14 alkyl methacrylate, manufactured by New Japan Chemical Co., Ltd. M-5300: Aronix M-5300, ω-carboxy-polycaprolactone monoacrylate, manufactured by Toa Synthetic <Paint composition Preparation of 1>
The alkyd-acrylic resin (paint resin) obtained above was used as a paint dispersant to obtain a paint composition 1.

That is, 0.65 parts by mass of the alkyd-acrylic resin solution (nonvolatile content 56.0% by mass) obtained above (that is, 0.364 parts by mass of the alkyd-acrylic resin as a pigment dispersant) and as a base resin. Alkyd resin (solid content 58% by mass, mineral spirit 42% by mass, trade name Hariftal 764-58, manufactured by Harima Kasei Co., Ltd.) 64.30 parts by mass and mineral spirit as a solvent (LAWS; manufactured by Shell Chemicals Japan) 8. 39 parts by mass, titanium oxide JR-603 (manufactured by Teika) 19.86 parts by mass as a pigment, cobalt octylate / zirconium octylate mixture as a desiccant (solid content 54% by mass, mineral spirit 46% by mass, solid) Mass ratio (1 / 3.4)) 4.15 parts by mass and AS-A T-380-20BS as an anti-dripping agent (solid content 20% by mass, mineral spirit 80% by mass, manufactured by Ito Oil Co., Ltd.) ) 2.65 parts by mass and kneaded with a 3-roll mill to prepare a coating composition 1.

<Preparation of paint composition 2>
The alkyd-acrylic resin (paint resin) obtained above was used as a paint base resin to obtain a paint composition 2.

That is, 64.95 parts by mass (that is, 36.37 parts by mass of the alkido-acrylic resin as the base resin) of the solution of the alkido-acrylic resin obtained above (nonvolatile content 56.0% by mass) and minerals as the solvent. 8.39 parts by mass of spirit, 19.86 parts by mass of titanium oxide JR-603 (manufactured by Teika) as a pigment, and a cobalt octylate / zirconium octylate mixture as a desiccant as a desiccant (solid content 54% by mass, Mineral spirit 46% by mass, solid content mass ratio (1 / 3.4)) 4.15 parts by mass, AS-A T-380-20BS as an anti-dripping agent (solid content 20% by mass, mineral spirit 80) (% by mass, manufactured by Ito Oil Co., Ltd.) 2.65 parts by mass was mixed and kneaded with a 3-roll mill to prepare a coating composition 2.

Examples 2-12 and Comparative Examples 1-3
An alkyd-acrylic resin (paint resin) was synthesized in the same manner as in Example 1 except that the formulation of the polymerizable monomer component in the synthesis of the alkyd-acrylic resin was changed to the formulations shown in Tables 3 to 5, and the alkyd was used. -Acrylic resin was used to obtain a coating composition 1 and a coating composition 2.

In Comparative Example 3, the alkyd-acrylic resin was not used.

Specifically, in Comparative Example 3, the coating composition 1 was prepared using 64.95 parts by mass of the alkyd resin as the base resin without using the alkyd-acrylic resin as the pigment dispersant. In addition, no alkyd-acrylic resin was used as the base resin. That is, the paint composition 2 was not prepared.

Tables 3 to 5 also show the molar concentration (mol / kg) of the (D) carboxyl group-terminated-monofunctional (meth) acrylic compound with respect to the total amount of the polymerizable monomer component.

<Evaluation>
The dilutability and compatibility of the paint resin are evaluated by the following methods, the dispersibility when the paint resin is used as the paint dispersant is evaluated, and further, the drying when the paint resin is used as the paint base resin is evaluated. Gender was evaluated. The results are shown in Tables 3-5.

(1) Dilution with a weak solvent First, 5 g of a sample was collected in a 50 mL sample tube, mineral spirit was added dropwise while adjusting the temperature to 25 ° C., and the mixture was stirred with a glass rod. Then, by repeating this operation up to the dilution limit, the dilutability (solubility) of the coating resin in a weak solvent was evaluated.

The liquid temperature was measured by putting the mercury temperature system directly into the 50 mL sample tube. The end point of the titration was when the liquid became turbid and a precipitate was formed.

Then, the dilution evaluation value was calculated by the following formula to evaluate the dilution.

Dilution evaluation value = Amount of mineral spirit used (mL) / Sampling amount (5 g)
The evaluation criteria are as follows.
A: Dilution evaluation value is 10 or more B: Dilution evaluation value is 2 or more and less than 10 C: Dilution evaluation value is less than 2 (2) Compatibility with other resins Paint resin and other resin, other A mixed varnish was prepared by mixing at a ratio of resin / paint resin = 9/1 (mass ratio).

Then, the obtained varnish was applied to a glass plate with a 4 mil applicator, and the solvent was evaporated to form a coating film. Then, the degree of cloudiness of the obtained coating film was measured using a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.).

This evaluated the compatibility with other resins.

Other resins include long oil alkyd resin (trade name: Hariftal 764-58, manufactured by Harima Kasei Co., Ltd.), alkyd-modified acrylic resin (trade name: Hariacron 8283-F1, manufactured by Harima Kasei Co., Ltd.), acrylic resin (trade name: Hariacron 7819). -F8, manufactured by Harima Kasei Co., Ltd.) and urethane-modified alkyd resin (trade name: Hariftal SC-3050, manufactured by Harima Kasei Co., Ltd.) were used.

The evaluation criteria are as follows.
A: Transparency of the coating film is less than 1% B: Transparency of the coating film is 1% or more and less than 15% C: Transparency of the coating film is 15% or more (3) Dispersibility Obtained in each Example and each Comparative Example. After the coating film composition 1 was stored at room temperature for 10 days, the separation state of the pigment was visually observed.

Then, the thickness of the separated and precipitated pigment layer (distance from the bottom of the bottle (cm)) and the liquid level height of the coating composition 1 (distance from the bottom of the bottle to the liquid level (cm)) are obtained. , The dispersibility evaluation value was calculated by the following formula to evaluate the dispersibility.

Dispersibility evaluation value = [Thickness of pigment layer (cm) / Liquid level height of paint composition 1 (cm)] x 100
The evaluation criteria are as follows.
A +: Dispersibility evaluation value is 0 (there is no separated and precipitated pigment layer)
A: Dispersion evaluation value exceeds 0 and is less than 1 B: Dispersion evaluation value is 1 or more and less than 5 C: Dispersion evaluation value is 5 or more (4) Dryness JIS K 5600-1-1 (1999) The dryness was evaluated by the following method in which the <general test (conditions and method)> of) was partially modified.

That is, the coating composition 2 obtained in each Example and each Comparative Example was coated on a glass plate (150 mm × 70 mm) having a thickness of 3 mm using a film applicator AP250 (manufactured by Taiyu Equipment Co., Ltd.).

Then, the painted glass plate was allowed to stand in a room at 23 ° C. and 50% RH, and the dry state after 24 hours was evaluated.

The evaluation criteria are as follows.
A +: The center of the coated surface is strongly sandwiched between the thumb and index finger, the coated surface does not have dents due to fingerprints, the movement of the coating film is not felt, and the center of the coated surface is rapidly and repeatedly rubbed with the fingertips. A state in which no scratches are left on the coated surface (cured and dried).
A: Gently and lightly rub the center of the coated surface with your fingertips so that no scratches are left on the coated surface (semi-curing and drying).
B: Lightly touch the center of the coated surface with your fingertips to keep your fingertips clean (dry to the touch).

The details of the abbreviations in the table are shown below.

N-Gerve CM-275: Alkyl methacrylate, mixture of C12 alkyl methacrylate and C14 alkyl methacrylate, manufactured by New Japan Chemical Co., Ltd. M-5300: Aronix M-5300, ω-carboxy-polycaprolactone monoacrylate, manufactured by Toagosei

Claims (11)

A paint resin containing an alkyd-acrylic resin.
The alkyd-acrylic resin is
An alkyd resin having an oxidatively polymerizable group and
It is a graft polymer with a polymerizable monomer component that can be graft-polymerized with the alkyd resin.
The polymerizable monomer component is
(A) Ring structure-containing (meth) acrylate and
(B) Alkyl (meth) acrylate having an alkyl group having 10 to 35 carbon atoms and
(C) Styrene and
(D) A coating resin containing at least one of a carboxyl group-terminated-monofunctional (meth) acrylic compound represented by the following (d1) to (d3).
(D1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1)
(In the formula (1), R ¹ represents a hydrogen atom and a methyl group, and n represents 1 to 10).
(D2) An acid anhydride modified product of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).
CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2)
(In the formula (2), R ¹ represents a hydrogen atom and a methyl group, R ² represents at least one selected from the group consisting of an ethylene group, a propylene group and a tetramethylene group, and n represents 1 to 1. 10 is shown.)
(D3) An acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).
CH ₂ = C (R ¹ ) COO ( _Cm H _2m O) _n H (3)
(In formula (3), R ¹ represents a hydrogen atom and a methyl group, m represents 2 to 4, and n represents 1 to 10.) (D) The carboxyl group-terminated-monofunctional (meth) acrylic compound is
(D1) The coating resin according to claim 1, further comprising a caprolactone adduct of (meth) acrylic acid represented by the above formula (1). The polymerizable monomer component further
The coating resin according to claim 1 or 2, wherein it contains a carboxyl group-containing polymerizable monomer (however, (D) the carboxyl group terminal-monofunctional (meth) acrylic compound is excluded). The polymerizable monomer component further
The coating resin according to any one of claims 1 to 3, which contains a hydroxyl group-containing polymerizable monomer. The polymerizable monomer component further
The coating resin according to any one of claims 1 to 4, which contains a tertiary amino group-containing polymerizable monomer and / or a quaternary ammonium group-containing polymerizable monomer. With respect to the total amount of the polymerizable monomer component
(D) Any one of claims 1 to 5, wherein the content ratio of the carboxyl group terminal-monofunctional (meth) acrylic compound is 0.5% by mass or more and 3.0% by mass or less. The paint resin described in. With respect to 100 parts by mass of the total amount of the polymerizable monomer component
The coating resin according to any one of claims 1 to 6, wherein the alkyd resin is 1 part by mass or more and 7 parts by mass or less. A paint dispersant containing the paint resin according to any one of claims 1 to 7. A paint-based resin comprising the paint resin according to any one of claims 1 to 7. A coating composition comprising the coating resin according to any one of claims 1 to 7. A coating film, which is a cured product of the coating composition according to claim 10.